EP0776767B1 - Ink-jet recording sheet and a method for its preparation - Google Patents
Ink-jet recording sheet and a method for its preparation Download PDFInfo
- Publication number
- EP0776767B1 EP0776767B1 EP19960118788 EP96118788A EP0776767B1 EP 0776767 B1 EP0776767 B1 EP 0776767B1 EP 19960118788 EP19960118788 EP 19960118788 EP 96118788 A EP96118788 A EP 96118788A EP 0776767 B1 EP0776767 B1 EP 0776767B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- starch
- ink
- paper
- recording sheet
- derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 36
- 238000002360 preparation method Methods 0.000 title description 2
- 229920002472 Starch Polymers 0.000 claims description 72
- 235000019698 starch Nutrition 0.000 claims description 72
- 239000008107 starch Substances 0.000 claims description 64
- 238000004513 sizing Methods 0.000 claims description 24
- 230000002209 hydrophobic effect Effects 0.000 claims description 23
- 229920000881 Modified starch Polymers 0.000 claims description 22
- 235000019426 modified starch Nutrition 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 125000001033 ether group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 239000000123 paper Substances 0.000 description 57
- 239000003153 chemical reaction reagent Substances 0.000 description 19
- 239000002585 base Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 240000008042 Zea mays Species 0.000 description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 8
- 235000005822 corn Nutrition 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 238000007641 inkjet printing Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- -1 for example Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 3
- 239000008120 corn starch Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920000856 Amylose Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012431 aqueous reaction media Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- KCYQMQGPYWZZNJ-BQYQJAHWSA-N hydron;2-[(e)-oct-1-enyl]butanedioate Chemical compound CCCCCC\C=C\C(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-BQYQJAHWSA-N 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229920001685 Amylomaize Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical class O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000007928 imidazolide derivatives Chemical class 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
Definitions
- This invention is directed to the production of improved recording materials for use in ink-jet printing. More particularly, the present invention relates to the method of preparing ink-jet recording or printing sheets, such as paper, that are coated with a selected hydrophobic starch applied at a high (low-shear) viscosity.
- Ink-jet printing of paper can be achieved through two general methods.
- the first type is the continuous stream method, where a continuous stream of ink is jetted through a small nozzle (typically about 50 ⁇ m (microns) in diameter) onto a substrate.
- the stream is perturbed, causing it to break into droplets at a fixed distance from the orifice.
- the droplets are guided to a specific location on the recording material by electrodes that charge the passing droplets, or are deflected to a gutter for reevaluation and reuse. This process is described in U.S. Patent Nos. 4,255,754; 4,698,123 and 4,751,517.
- the second type of ink-jet printing is called "drop-on-demand".
- a droplet is expelled from an orifice of an ink-jet printer directly to a position on a recording medium, but only when needed ("on demand").
- One type of drop-on demand printing method uses a piezoelectric transducer to produce pressure pulses to expel the ink drops.
- a second type of drop-on-demand printing method uses thermal action induced by a heat generating resistor near the nozzle to generate drops as needed. This method has been described as the "bubble jet” method and is described in U.S. Patent Nos. 4,500,895; 4,513,298 and 4,794,409.
- the ink-receiving layers on ink-jet recording materials must meet demanding and often conflicting requirements.
- the ink-receiving layers must readily absorb the ink, but not allow the dots of ink applied to expand more than necessary to obtain an image with high optical density.
- the ink-receiving layer must also rapidly absorb the ink applied so that it will not feather or smudge when touched soon after application, but not allow the ink to penetrate so far as to show through the other side of the recording element.
- ink-receptive layers have been disclosed in the prior art. While some of these ink-receptive layers meet the above listed demands of ink-jet recording, they are usually very expensive and require unusual or extensive processing.
- the most effective types of ink-receptive coatings include high surface area pigments such as fumed silicas or hydrated aluminas that are bound with polymers such as polyvinyl alcohol or polyvinyl pyrrolidone. While these combinations of polymers and pigments are effective in improving the quality of ink-jet prints made on recording materials, they are very expensive, are difficult to disperse and their coatings are very difficult to dry after application on paper. This oftentimes necessitates their application on slow, off-machine coaters which further increases the cost of the recording media containing them. Ink-jet paper coated with such expensive pigments typically sell for ten times the price of a high quality copy paper.
- Starch a relatively inexpensive material, is well known as a coating or surface size for paper.
- starch alone has not been able to significantly enhance ink-jet print quality.
- Expensive synthetic chemicals are often added to starch to increase the hydrophobicity of the paper surface.
- the ability to apply starch in conventional size presses under different conditions, particularly high viscosity has been limited because of what has been termed poor "runnability”.
- Starches have typically been used to coat or surface size paper by passing the paper through the nip formed between two rolls. When using starch at high viscosities, undesirable running conditions such as "nip rejection" develop. Nip rejection is simply the spitting or rejection of the starch cook from the press nip between the rotating size press rolls during operation of the paper machine.
- Starch that spits from the nip can land on the dryer cans situated after the size press, causing the sheet to stick to these cans and tear. Also, this starch can land on the sheet after the size press and cause uneven pickup on the sheet resulting in uneven and poor print quality across the sheet surface.
- hydrophobic starch derivatives can be applied at a high viscosity to coat or surface size an ink-jet recording material and provide significantly improved printing quality. More particularly, this invention involves a method for preparing an ink-jet recording sheet with improved ink-jet print quality comprising:
- This invention involves two significant aspects. First, that the use of the selected hydrophobic starch derivatives, as defined herein, can be applied using conventional paper machine size presses at viscosities higher than those previously considered to be operable or runnable. Second, and most important, when applied at these high viscosities, significant and unexpected improvements are obtained in the ink-jet print quality of the coated or surface sized recording sheets.
- the hydrophobic starch derivatives used in this invention are starch ester or ether derivatives wherein the ester or ether substituent comprises a saturated or unsaturated hydrocarbon chain of 6 to 22 carbon atoms, preferably 8 to 20 carbon atoms. It should be understood that the hydrocarbon chain may contain some branching. It should also be understood that the ester or ether substituent may contain other groups in addition to the hydrocarbon chain as long as such groups do not interfere with the hydrophobic properties of the substituent.
- the hydrocarbon or hydrophobic substituent group may be alkyl, alkenyl, aryl, aralkyl or aralkenyl with alkyl and alkenyl being preferred.
- the base starch material used herein may be any of several granular starches, native or converted. Such starches include those derived from any plant source including corn, potato, wheat, rice, sago, tapioca, waxy maize, sorghum and high amylose starch such as high amylose corn, i.e., starch having at least 40% and more particularly at least 65% amylose content by weight, etc. Starch flours may also be used. Also included are the conversion products derived from any of the former bases such as, for example, dextrins prepared by hydrolytic action of acid and/or heat; fluidity or thin boiling starches prepared by enzyme conversions or mild acid hydrolysis; and oxidized starches prepared by treatment with oxidants such as sodium hypochlorite.
- hydrophobic starch derivatives used in this invention are prepared by reacting starch with selected reagents.
- a suitable class of reagents for preparing esters useful herein include substituted cyclic dicarboxylic acid anhydrides such as those described in U.S. Patent No. 2,661,349 (issued on December 1, 1953 to Caldwell et al.) having the structure: wherein R is a dimethylene or trimethylene radical and R 1 comprises a hydrocarbon chain of at least 6, more particularly 6 to 22 and preferably 8 to 20 carbon atoms.
- the substituent R 1 group may be alkyl, alkenyl, aryl, aralkyl or aralkenyl with alkyl and alkenyl being preferred.
- the substituted cyclic dicarboxylic acid anhydrides falling within the above structural formula are the substituted succinic and glutaric acid anhydrides.
- other substituent groups such as sulfonic acid or lower alkyl groups which would not affect sizing performance may be present.
- Another suitable class of reagents for preparing derivatives useful herein include the imidazolides or N,N'-disubstituted imidazolium salts of carboxylic or sulfonic acids such as those described in U.S. Patent No. Re 28,809 (issued May 11, 1976 to M. Tessler) which is a reissue of U.S. Patent No. 3,720,663 (issued on March 13, 1973 to M. Tessler) and U.S. Patent No. 4,020,272 (issued April 26, 1977 to M. Tessler) having the general formula: wherein Z is or - SO 2 -.
- A comprises a hydrocarbon chain of at least 6, more particularly 6 to 22, preferably 8 to 20 carbon atoms.
- R 2 is H or C 1 -C 4 alkyl.
- R 3 is C 1 -C 4 alkyl
- X - is an anion.
- a third class of reagents useful herein include the etherifying reagents described in U.S. Patent No. 2,876,217 (issued on March 3, 1959 to E. Paschall) comprising the reaction product of an epihalohydrin with a tertiary amine having the structure: wherein R 4 and R 5 are independently H or a C 1 -C 4 alkyl and A 1 comprises a hydrocarbon chain of at least 6, more particularly 6 to 22, preferably 8 to 20 carbon atoms.
- the starch esterification or etherification reactions may be conducted by a number of techniques known in the art and discussed in the literature employing, for example, an aqueous reaction medium, an organic solvent medium, or a dry heat reaction technique. See, for example, R. L. Whistler, Methods in Carbohydrate Chemistry, Vol. IV, 1964, pp. 279-311; R. L. Whistler et al., Starch, Chemistry and Technology, Second Edition, 1984, pp. 311-366; and R. Davidson and N. Sittig, Water-Soluble Resins, Second Edition, 1968, Chapter 2.
- the starch derivatives herein are preferably prepared employing an aqueous reaction medium at temperatures between 20° and 45°C.
- the starch derivatives may be produced either in gelatinized or ungelatinized form.
- the advantage of having the derivative in ungelatinized form is that it may be filtered, washed, dried and conveyed to the mill in the form of a dry powder.
- starch When employing the cyclic dicarboxylic acid anhydride reagents, starch is preferably treated in granular form with the reagents in an aqueous alkali medium at a pH not lower than 7 nor higher than 11. This may be accomplished by suspending the starch in water, to which has been added (either before or after the addition of the starch) sufficient base such as alkali metal hydroxide, alkaline earth hydroxide, quaternary ammonium hydroxide, or the like, to maintain the mixture in an alkaline state during the reaction. The required amount of the reagent is then added, agitation being maintained until the desired reaction is complete.
- sufficient base such as alkali metal hydroxide, alkaline earth hydroxide, quaternary ammonium hydroxide, or the like
- Heat may be applied, if desired, in order to speed the reaction; however, if heat is used, temperatures of less than about 40°C should be maintained.
- the alkali and the anhydride reagent are added concurrently to the starch slurry, regulating the rate of flow of each of these materials so that the pH of the slurry remains preferably between 8 and 11.
- the reagents react with starch in only minor amounts in standard aqueous reactions.
- starch is reacted with the hydrophobic reagent under standard aqueous conditions in the presence of at least 5%, preferably 7 to 15% (based on the weight of the reagent), of a water-soluble organic quaternary salt which is employed as a phase transfer agent.
- the organic salts of which trioctylmethyl ammonium chloride or tricaprylylmethyl ammonium chloride are preferably employed, are described in U.S. Patent No. 3,992,432 (issued November 16, 1976 to D. Napier et al.)
- the proportion of etherifying or esterifying reagent used will vary with the particular reagent chosen (since they naturally vary in reactivity and reaction efficiency), and the degree of substitution desired. Thus, substantial improvements in sizing efficiency and ink-jet print quality have been achieved by using a derivative made with at least 2% of the reagent, based on the weight of the starch.
- the upper limit of treatment will vary and is limited only by the solubility or dispersibility of the final product. Generally the maximum level will be less than 25%. More particularly, from about 2 to 20%, preferably about 3 to 15% and more preferably about 3 to 10% by weight of reagent based on the weight of the starch is used to prepare the starch derivative.
- the starch derivatives used in this invention can be better defined as those starches having a degree of substitution (DS) of from about 0.02 to 0.1, more particularly from 0.03 to 0.1 and preferably from about 0.03 to 0.07.
- degree of substitution indicates the average number of sites per anhydroglucose unit of the starch molecule on which there are substituted groups.
- Viscosity of the starch derivative is important consideration in the successful application of the selected hydrophobic starch derivatives as described herein, in the preparation of high quality ink-jet recording material.
- Particularly useful viscosities at which the hydrophobic starch derivatives have been found to provide operable or runnable size press conditions as well as improved ink-jet quality in the coated recording sheets are Brookfield viscosities of at least 50 cps and more particularly 50 to 500 mPa.s (cps) at 65°C.
- the viscosity will be 100 to 300 mPa.s (cps) Brookfield at 65°C. This viscosity was determined using a Brookfield Viscometer (Model LVDV-III), fitted with an SC4-21 spindle at 100 rpm and 65°C (150°F).
- the viscosity chosen will depend on the speed of the paper machine; higher viscosities are applicable to slower paper machines while the lower range of viscosity is more suited to the faster paper machines.
- Paper machine speeds typically are in the range of from about 2,54 to 15,24 m/s (500 to 3000 ft/min) and more particularly from about 4,064 to 7,62 m/s (800 to 1500 ft/min.)
- hydrophobic starch derivatives can be effectively applied to the surface of a previously prepared paper or paperboard web by means of any conventional surface sizing technique.
- surface sizing is accomplished by passing the web of paper in a vertical direction downward between a pair of press rolls. In the nip between these rolls, a flow of surface size solution is directed in such a manner as to form ponds on both sides of the paper. As the paper moves between the rolls, excess surface size solution is metered off. The sized web is then dried by means of any conventional drying operation selected by the practitioner.
- the amount of hydrophobic starch derivative to be used in an aqueous dispersion will be from about 3 to 20% and more preferably from about 5 to 12% by weight. Whatever starch composition or method of application, it will be sufficient to provide a pick-up of the starch derivative of from about 2 to 10% by weight, preferably 3 to 7%, based on the dry paper weight. Within the mentioned range, the precise amount of the size or starch derivative will depend for the most part upon the type of pulp which is being treated, the particular grade of ink-jet printing paper being manufactured, the specific operating conditions, as well as the particular end use for which the paper product is destined.
- the selected hydrophobic starch derivatives may be successfully utilized for the surface sizing or coating of various substrate materials which are used in providing ink-jet recording sheets or paper.
- Suitable substrates include paper and thermoplastic resin films and other material useful in transparencies.
- Paper which is the most common substrate is prepared from both cellulosic and combinations of cellulosic with noncellulosic fibers.
- the hardwood or softwood cellulosic fibers which may be used include bleached and unbleached sulfate (Kraft), bleached and unbleached sulfite, bleached and unbleached soda, neutral sulfite semi-chemical, chemi-groundwood, and any combination of these fibers.
- All types of paper dyes and tints, pigments and fillers may be added to the paper (in the usual manner) which is to be sized or coated by the starch dispersion according to the present invention.
- Such materials include clay, talc, titanium dioxide, calcium carbonate, calcium sulfate, silicas and diatomaceous earths.
- the paper can contain other additives, including rosin, alum, and internal sizing compositions such as alkenyl succinic anhydride and alkyl ketene dimer.
- Other surface sizing agents as well as pigments, dyes and lubricants can also be used in conjunction with the size described herein.
- the added materials as described above may be used, as long as they do not detrimentally effect the sizing and hydrophobic properties of the prepared ink-jet recording sheet or the ink-jet printing quality of the sheet as well as the operability of the papermaking operation.
- Alkaline paper is generally prepared in wet end systems having a pH of from 7.5 to 10.5 and more particularly 7.5 to 9.0. Alkaline paper often contains significant amounts of calcium carbonate, for example 1 to 30% by weight. It is also noted that the alkaline paper substrates useful in this invention will not contain any multivalent metal ions.
- OSA octenyl succinic acid anhydride waxy starch
- An OSA (octenyl succinic acid anhydride) waxy starch was prepared in the following manner. About 100 parts of waxy starch was slurried in 150 parts of water and the pH adjusted to 7.5 by the addition of dilute sodium hydroxide (3%). A total of 3 parts octenyl succinic acid anhydride (OSA) reagent was slowly added to the agitated starch slurry with the pH maintained at 7.5 by the metered addition of the dilute sodium hydroxide. After the reaction was complete the pH was adjusted to about 5.5 with dilute hydrochloric acid (3 : 1). The starch was thereafter recovered by filtration, washed three times with water and air dried. The final product had an OSA content of about 2.5%.
- OSA octenyl succinic acid anhydride
- a sample of the prepared starch, i.e., 10% solids 40 WF OSA waxy starch was applied to the surface of an unsurface sized alkaline fine paper.
- WF refers to water fluidity and was measured using a Thomas Rotational Shear-Type Viscometer (manufactured by Arthur H. Thomas Co., Philadelphia, PA) in accordance with standard procedures such as disclosed in U.S. Patent No. 4,499,116 issued February 12, 1985 to Zwiercan et al.
- Another sample of conventional 80 WF hydroxyethylated corn starch was also applied to an unsurface sized alkaline fine paper.
- the surface sizing application was performed using a size press simulator composed of two heated, rubber-coated stainless steel rolls that were arranged in the format of a horizontal size press, where paper is fed vertically through the nip between the rolls.
- a pond of the surface size starch (pre-heated to 65.6°C) was recirculated between the rolls at a rate of 33,33 cm 3 /s (2 liters/minute) in order to maintain a pond in the nip between the rolls.
- Gurley Density is a measure of the air resistance (or porosity) of a sized paper sheet, which is conducted in accordance with TAPPI Standard Method T 460-OM-86, entitled "Air Resistance of Paper". Briefly, a sample of the sized paper having an area of 1 in 2 (6.45 cm 2 ) is placed at the outlet end of an apparatus containing an open cylinder filled with air at ambient pressure (1 atm). The air is then forcibly expelled through the paper under the weight of the cylinder; the time for 100 cc of air to pass through the sample is recorded.
- Time for 100 cc of air to pass through the sample is a relative measure of paper porosity, and the more porous papers will have lower Gurley Density times. In general, the better externally sized paper will have lower porosity (or higher Gurley Density test times).
- This continuous film being comprised of a generally ink receptive polymer, would be more able to capture the ink droplets as they are applied to the paper, preventing their migration through the Z-direction (or thickness) of the paper as well as preventing migration along the papers surface (also called feathering).
- an alkaline base stock having an internal sizing level of 200 seconds (as per TAPPI Test Method T 530 pm - 89, "Size Test For Paper by Ink Resistance (“Hercules Method”)) was surface-sized with 10% dispersions of both a hydroxyethylated corn as well as a 55 WF waxy starch reacted with 5% of DDSA (dodecenyl succinic anhydride).
- the alkaline base stock surface sized with the 80 WF hydroxyethylated corn Compared to the alkaline base stock surface sized with the 80 WF hydroxyethylated corn, the alkaline base stock surface sized with the 55 WF DDSA waxy gave over ten times higher density value in seconds (as per TAPPI T460).
- the alkaline base stock surface sized with the 80 WF oxidized corn starch gave nearly twice the density value in seconds (as per TAPPI T460).
- This example indicates that paper surface-sized with a layer comprised of a starch substituted with selected hydrophobic groups that is applied at a low-shear viscosity of at least 50 mPa.s (cps at 65°C)) will reduce paper porosity, as compared to paper surface-sized with starches that are not substituted with such groups.
- surface-sizing was performed with blends of cationic starch (reacted with a tertiary amine group) (Cat.) and a starch reacted with OSA.
- the nitrogen level (of the cationic starches), the OSA level, the percent of cationic starch in the blend (the balance of the blend is the percent of OSA-treated starch), the fluidity (WF) of the cationic, the WF of the OSA (or hydrophobic) starch and the percent solids of the dispersion applied to the paper were varied as per a two-factor experimental design.
- the sample sized paper sheets were then evaluated as follows. Gurley density was determined for each sample sheet as in Example 1.
- Sample sheets were printed on a Hewlett-Packard DeskJet 500C ink-jet printer using a test pattern provided by Hewlett-Packard. On this pattern were a series of three 1 inch squares, two of which were presented at maximum coverage of ink (100%). The optical density for each sample sheet was measured on a MacBeth Densitometer with the results shown below.
- This test data shows that a hydrophobically modified starch, in accordance with this invention, reduces paper porosity (Gurley Density) when applied at higher Brookfield viscosities. Additionally, this data shows that the optical density of a solid black printed box was highest when only the hydrophobically substituted starch was used at a high viscosity in place of a blend of cationic starch and hydrophobically substituted starch. Blends of cationic and hydrophobic starch, even when applied at a viscosity above 50 cps, did not improve the optical density of the black area, compared to the unsurface-sized base sheet.
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Description
- This invention is directed to the production of improved recording materials for use in ink-jet printing. More particularly, the present invention relates to the method of preparing ink-jet recording or printing sheets, such as paper, that are coated with a selected hydrophobic starch applied at a high (low-shear) viscosity.
- Ink-jet printing of paper can be achieved through two general methods. The first type is the continuous stream method, where a continuous stream of ink is jetted through a small nozzle (typically about 50 µm (microns) in diameter) onto a substrate. The stream is perturbed, causing it to break into droplets at a fixed distance from the orifice. The droplets are guided to a specific location on the recording material by electrodes that charge the passing droplets, or are deflected to a gutter for reevaluation and reuse. This process is described in U.S. Patent Nos. 4,255,754; 4,698,123 and 4,751,517.
- The second type of ink-jet printing is called "drop-on-demand". In this method, a droplet is expelled from an orifice of an ink-jet printer directly to a position on a recording medium, but only when needed ("on demand"). One type of drop-on demand printing method uses a piezoelectric transducer to produce pressure pulses to expel the ink drops. A second type of drop-on-demand printing method uses thermal action induced by a heat generating resistor near the nozzle to generate drops as needed. This method has been described as the "bubble jet" method and is described in U.S. Patent Nos. 4,500,895; 4,513,298 and 4,794,409.
- The ink-receiving layers on ink-jet recording materials must meet demanding and often conflicting requirements. The ink-receiving layers must readily absorb the ink, but not allow the dots of ink applied to expand more than necessary to obtain an image with high optical density. The ink-receiving layer must also rapidly absorb the ink applied so that it will not feather or smudge when touched soon after application, but not allow the ink to penetrate so far as to show through the other side of the recording element.
- To meet these requirements, many variations in ink-receptive layers have been disclosed in the prior art. While some of these ink-receptive layers meet the above listed demands of ink-jet recording, they are usually very expensive and require unusual or extensive processing. The most effective types of ink-receptive coatings include high surface area pigments such as fumed silicas or hydrated aluminas that are bound with polymers such as polyvinyl alcohol or polyvinyl pyrrolidone. While these combinations of polymers and pigments are effective in improving the quality of ink-jet prints made on recording materials, they are very expensive, are difficult to disperse and their coatings are very difficult to dry after application on paper. This oftentimes necessitates their application on slow, off-machine coaters which further increases the cost of the recording media containing them. Ink-jet paper coated with such expensive pigments typically sell for ten times the price of a high quality copy paper.
- Starch, a relatively inexpensive material, is well known as a coating or surface size for paper. However, starch alone has not been able to significantly enhance ink-jet print quality. Expensive synthetic chemicals are often added to starch to increase the hydrophobicity of the paper surface. Additionally, the ability to apply starch in conventional size presses under different conditions, particularly high viscosity, has been limited because of what has been termed poor "runnability". Starches have typically been used to coat or surface size paper by passing the paper through the nip formed between two rolls. When using starch at high viscosities, undesirable running conditions such as "nip rejection" develop. Nip rejection is simply the spitting or rejection of the starch cook from the press nip between the rotating size press rolls during operation of the paper machine. Starch that spits from the nip can land on the dryer cans situated after the size press, causing the sheet to stick to these cans and tear. Also, this starch can land on the sheet after the size press and cause uneven pickup on the sheet resulting in uneven and poor print quality across the sheet surface.
- What is needed is a starch based product that can be applied on a paper machine size press and provide improved ink-jet quality at low cost, without the need for the addition of expensive synthetic chemicals.
- It has now been found that selected hydrophobic starch derivatives can be applied at a high viscosity to coat or surface size an ink-jet recording material and provide significantly improved printing quality. More particularly, this invention involves a method for preparing an ink-jet recording sheet with improved ink-jet print quality comprising:
- a) providing a recording sheet substrate,
- b) forming a sizing composition comprising an aqueous dispersion of a hydrophobic starch ester or ether derivative wherein the ester or ether substituent comprises a saturated or unsaturated hydrocarbon chain of 6 to 22 carbon atoms and the starch containing sizing composition has a viscosity of at least 50 mPa.s (cps) Brookfield at 65°C,
- c) applying said sizing composition to said recording sheet substrate, and
- d) drying said substrate to provide an ink-jet recording sheet.
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- This invention involves two significant aspects. First, that the use of the selected hydrophobic starch derivatives, as defined herein, can be applied using conventional paper machine size presses at viscosities higher than those previously considered to be operable or runnable. Second, and most important, when applied at these high viscosities, significant and unexpected improvements are obtained in the ink-jet print quality of the coated or surface sized recording sheets.
- The hydrophobic starch derivatives used in this invention are starch ester or ether derivatives wherein the ester or ether substituent comprises a saturated or unsaturated hydrocarbon chain of 6 to 22 carbon atoms, preferably 8 to 20 carbon atoms. It should be understood that the hydrocarbon chain may contain some branching. It should also be understood that the ester or ether substituent may contain other groups in addition to the hydrocarbon chain as long as such groups do not interfere with the hydrophobic properties of the substituent. The hydrocarbon or hydrophobic substituent group may be alkyl, alkenyl, aryl, aralkyl or aralkenyl with alkyl and alkenyl being preferred.
- The base starch material used herein may be any of several granular starches, native or converted. Such starches include those derived from any plant source including corn, potato, wheat, rice, sago, tapioca, waxy maize, sorghum and high amylose starch such as high amylose corn, i.e., starch having at least 40% and more particularly at least 65% amylose content by weight, etc. Starch flours may also be used. Also included are the conversion products derived from any of the former bases such as, for example, dextrins prepared by hydrolytic action of acid and/or heat; fluidity or thin boiling starches prepared by enzyme conversions or mild acid hydrolysis; and oxidized starches prepared by treatment with oxidants such as sodium hypochlorite.
- The hydrophobic starch derivatives used in this invention are prepared by reacting starch with selected reagents.
- A suitable class of reagents for preparing esters useful herein include substituted cyclic dicarboxylic acid anhydrides such as those described in U.S. Patent No. 2,661,349 (issued on December 1, 1953 to Caldwell et al.) having the structure: wherein R is a dimethylene or trimethylene radical and R1 comprises a hydrocarbon chain of at least 6, more particularly 6 to 22 and preferably 8 to 20 carbon atoms. The substituent R1 group may be alkyl, alkenyl, aryl, aralkyl or aralkenyl with alkyl and alkenyl being preferred. The substituted cyclic dicarboxylic acid anhydrides falling within the above structural formula are the substituted succinic and glutaric acid anhydrides. In addition to the hydrocarbon chain substituent, other substituent groups such as sulfonic acid or lower alkyl groups which would not affect sizing performance may be present.
- Another suitable class of reagents for preparing derivatives useful herein include the imidazolides or N,N'-disubstituted imidazolium salts of carboxylic or sulfonic acids such as those described in U.S. Patent No. Re 28,809 (issued May 11, 1976 to M. Tessler) which is a reissue of U.S. Patent No. 3,720,663 (issued on March 13, 1973 to M. Tessler) and U.S. Patent No. 4,020,272 (issued April 26, 1977 to M. Tessler) having the general formula: wherein Z is or - SO2 -. A comprises a hydrocarbon chain of at least 6, more particularly 6 to 22, preferably 8 to 20 carbon atoms. R2 is H or C1-C4 alkyl. R3 is C1-C4 alkyl, and X- is an anion.
- A third class of reagents useful herein include the etherifying reagents described in U.S. Patent No. 2,876,217 (issued on March 3, 1959 to E. Paschall) comprising the reaction product of an epihalohydrin with a tertiary amine having the structure: wherein R4 and R5 are independently H or a C1-C4 alkyl and A1 comprises a hydrocarbon chain of at least 6, more particularly 6 to 22, preferably 8 to 20 carbon atoms.
- The starch esterification or etherification reactions may be conducted by a number of techniques known in the art and discussed in the literature employing, for example, an aqueous reaction medium, an organic solvent medium, or a dry heat reaction technique. See, for example, R. L. Whistler, Methods in Carbohydrate Chemistry, Vol. IV, 1964, pp. 279-311; R. L. Whistler et al., Starch, Chemistry and Technology, Second Edition, 1984, pp. 311-366; and R. Davidson and N. Sittig, Water-Soluble Resins, Second Edition, 1968, Chapter 2. The starch derivatives herein are preferably prepared employing an aqueous reaction medium at temperatures between 20° and 45°C.
- For use herein, the starch derivatives may be produced either in gelatinized or ungelatinized form. The advantage of having the derivative in ungelatinized form is that it may be filtered, washed, dried and conveyed to the mill in the form of a dry powder.
- When employing the cyclic dicarboxylic acid anhydride reagents, starch is preferably treated in granular form with the reagents in an aqueous alkali medium at a pH not lower than 7 nor higher than 11. This may be accomplished by suspending the starch in water, to which has been added (either before or after the addition of the starch) sufficient base such as alkali metal hydroxide, alkaline earth hydroxide, quaternary ammonium hydroxide, or the like, to maintain the mixture in an alkaline state during the reaction. The required amount of the reagent is then added, agitation being maintained until the desired reaction is complete. Heat may be applied, if desired, in order to speed the reaction; however, if heat is used, temperatures of less than about 40°C should be maintained. In a preferred method, the alkali and the anhydride reagent are added concurrently to the starch slurry, regulating the rate of flow of each of these materials so that the pH of the slurry remains preferably between 8 and 11.
- Due to the greater hydrophobic nature of certain of the substituted cyclic dicarboxylic acid anhydride reagents useful herein (i.e., those having C10 or higher substituents), the reagents react with starch in only minor amounts in standard aqueous reactions. In order to improve the starch reaction efficiency, starch is reacted with the hydrophobic reagent under standard aqueous conditions in the presence of at least 5%, preferably 7 to 15% (based on the weight of the reagent), of a water-soluble organic quaternary salt which is employed as a phase transfer agent. The organic salts, of which trioctylmethyl ammonium chloride or tricaprylylmethyl ammonium chloride are preferably employed, are described in U.S. Patent No. 3,992,432 (issued November 16, 1976 to D. Napier et al.)
- The proportion of etherifying or esterifying reagent used will vary with the particular reagent chosen (since they naturally vary in reactivity and reaction efficiency), and the degree of substitution desired. Thus, substantial improvements in sizing efficiency and ink-jet print quality have been achieved by using a derivative made with at least 2% of the reagent, based on the weight of the starch. Depending on the particular derivative being formed, the upper limit of treatment will vary and is limited only by the solubility or dispersibility of the final product. Generally the maximum level will be less than 25%. More particularly, from about 2 to 20%, preferably about 3 to 15% and more preferably about 3 to 10% by weight of reagent based on the weight of the starch is used to prepare the starch derivative. The starch derivatives used in this invention can be better defined as those starches having a degree of substitution (DS) of from about 0.02 to 0.1, more particularly from 0.03 to 0.1 and preferably from about 0.03 to 0.07. The term "degree of substitution" (DS) as used herein indicates the average number of sites per anhydroglucose unit of the starch molecule on which there are substituted groups.
- An important consideration in the successful application of the selected hydrophobic starch derivatives as described herein, in the preparation of high quality ink-jet recording material, is the viscosity of the starch derivative. Particularly useful viscosities at which the hydrophobic starch derivatives have been found to provide operable or runnable size press conditions as well as improved ink-jet quality in the coated recording sheets are Brookfield viscosities of at least 50 cps and more particularly 50 to 500 mPa.s (cps) at 65°C. Preferably the viscosity will be 100 to 300 mPa.s (cps) Brookfield at 65°C. This viscosity was determined using a Brookfield Viscometer (Model LVDV-III), fitted with an SC4-21 spindle at 100 rpm and 65°C (150°F).
- The viscosity chosen will depend on the speed of the paper machine; higher viscosities are applicable to slower paper machines while the lower range of viscosity is more suited to the faster paper machines. Paper machine speeds typically are in the range of from about 2,54 to 15,24 m/s (500 to 3000 ft/min) and more particularly from about 4,064 to 7,62 m/s (800 to 1500 ft/min.)
- In practice, it has been found that the hydrophobic starch derivatives can be effectively applied to the surface of a previously prepared paper or paperboard web by means of any conventional surface sizing technique. Included among these techniques are size press, tub, gate roll applicators and calendar stack sizing procedures. Thus, for example, in a size press technique surface sizing is accomplished by passing the web of paper in a vertical direction downward between a pair of press rolls. In the nip between these rolls, a flow of surface size solution is directed in such a manner as to form ponds on both sides of the paper. As the paper moves between the rolls, excess surface size solution is metered off. The sized web is then dried by means of any conventional drying operation selected by the practitioner.
- The amount of hydrophobic starch derivative to be used in an aqueous dispersion will be from about 3 to 20% and more preferably from about 5 to 12% by weight. Whatever starch composition or method of application, it will be sufficient to provide a pick-up of the starch derivative of from about 2 to 10% by weight, preferably 3 to 7%, based on the dry paper weight. Within the mentioned range, the precise amount of the size or starch derivative will depend for the most part upon the type of pulp which is being treated, the particular grade of ink-jet printing paper being manufactured, the specific operating conditions, as well as the particular end use for which the paper product is destined.
- The selected hydrophobic starch derivatives may be successfully utilized for the surface sizing or coating of various substrate materials which are used in providing ink-jet recording sheets or paper. Suitable substrates include paper and thermoplastic resin films and other material useful in transparencies. Paper which is the most common substrate is prepared from both cellulosic and combinations of cellulosic with noncellulosic fibers. The hardwood or softwood cellulosic fibers which may be used include bleached and unbleached sulfate (Kraft), bleached and unbleached sulfite, bleached and unbleached soda, neutral sulfite semi-chemical, chemi-groundwood, and any combination of these fibers. These designations refer to wood pulp fibers which have been prepared by means of a variety of processes which are used in the pulp and paper industry. In addition, synthetic cellulose fibers of the viscose rayon or regenerated cellulose type can also be used, as well as recycled waste papers from various sources.
- All types of paper dyes and tints, pigments and fillers may be added to the paper (in the usual manner) which is to be sized or coated by the starch dispersion according to the present invention. Such materials include clay, talc, titanium dioxide, calcium carbonate, calcium sulfate, silicas and diatomaceous earths. The paper can contain other additives, including rosin, alum, and internal sizing compositions such as alkenyl succinic anhydride and alkyl ketene dimer. Other surface sizing agents as well as pigments, dyes and lubricants can also be used in conjunction with the size described herein. The added materials as described above may be used, as long as they do not detrimentally effect the sizing and hydrophobic properties of the prepared ink-jet recording sheet or the ink-jet printing quality of the sheet as well as the operability of the papermaking operation.
- While the base paper used can be acid or alkaline grade, the greatest improvement in ink-jet printing quality will be seen on alkaline paper grades. Alkaline paper is generally prepared in wet end systems having a pH of from 7.5 to 10.5 and more particularly 7.5 to 9.0. Alkaline paper often contains significant amounts of calcium carbonate, for example 1 to 30% by weight. It is also noted that the alkaline paper substrates useful in this invention will not contain any multivalent metal ions.
- The following examples further illustrate the embodiments of this invention. In these examples, all parts are given by weight and all temperatures in degrees Celsius unless otherwise noted.
- The ability of a starch reacted with hydrophobic reagent groups to reduce paper porosity compared to a conventional surface size starch was shown as follows.
- An OSA (octenyl succinic acid anhydride) waxy starch was prepared in the following manner. About 100 parts of waxy starch was slurried in 150 parts of water and the pH adjusted to 7.5 by the addition of dilute sodium hydroxide (3%). A total of 3 parts octenyl succinic acid anhydride (OSA) reagent was slowly added to the agitated starch slurry with the pH maintained at 7.5 by the metered addition of the dilute sodium hydroxide. After the reaction was complete the pH was adjusted to about 5.5 with dilute hydrochloric acid (3 : 1). The starch was thereafter recovered by filtration, washed three times with water and air dried. The final product had an OSA content of about 2.5%.
- A sample of the prepared starch, i.e., 10% solids 40 WF OSA waxy starch was applied to the surface of an unsurface sized alkaline fine paper. "WF" refers to water fluidity and was measured using a Thomas Rotational Shear-Type Viscometer (manufactured by Arthur H. Thomas Co., Philadelphia, PA) in accordance with standard procedures such as disclosed in U.S. Patent No. 4,499,116 issued February 12, 1985 to Zwiercan et al. Another sample of conventional 80 WF hydroxyethylated corn starch was also applied to an unsurface sized alkaline fine paper.
- The surface sizing application was performed using a size press simulator composed of two heated, rubber-coated stainless steel rolls that were arranged in the format of a horizontal size press, where paper is fed vertically through the nip between the rolls. A pond of the surface size starch (pre-heated to 65.6°C) was recirculated between the rolls at a rate of 33,33 cm3/s (2 liters/minute) in order to maintain a pond in the nip between the rolls. An alkaline base stock containing 5.4% precipitated calcium carbonate (PCC) filler and having an internal sizing level of 49 seconds (as per TAPPI Test Method T530 pm - 89, "Size Test for Paper by Ink Resistance ("Hercules Method:)) was attached to a 1 meter long unbleached kraft leader sheet. The leader was placed between 1 meter long unbleached kraft leader sheet. The leader was placed between the rolls, the size press solution recirculation pump was started, then the motor driving the size press rolls was turned on, accelerating to a speed of 100 meters/minute by the time the alkaline base stock reached the size press nip. The then surface-sized sheet was removed from the leader and dried on a photographic-type drum drier. The final sheet was cut to 0,2159 x 0,2794 m (8½ x 11 inches.)
- Each sheet's porosity was evaluated using TAPPI Method T460. This test gives what is called "Gurley Density" and is performed as follows:
- Gurley Density - this test is a measure of the air resistance (or porosity) of a sized paper sheet, which is conducted in accordance with TAPPI Standard Method T 460-OM-86, entitled "Air Resistance of Paper". Briefly, a sample of the sized paper having an area of 1 in2 (6.45 cm2) is placed at the outlet end of an apparatus containing an open cylinder filled with air at ambient pressure (1 atm). The air is then forcibly expelled through the paper under the weight of the cylinder; the time for 100 cc of air to pass through the sample is recorded.
- Time for 100 cc of air to pass through the sample is a relative measure of paper porosity, and the more porous papers will have lower Gurley Density times. In general, the better externally sized paper will have lower porosity (or higher Gurley Density test times).
- The sized paper was then subjected to the above determinations. The results of this analysis is given in the table below (average of two sheets for each surface size starch type).
Starch Description % Solids 65°C Brookfield (cps) mPa.s Gurley Density - Seconds (as per TAPPI T460) 80 WF hydroxyethylated corn 10.0 32 11.5 40 WF OSA Waxy 10.0 120 30.0 - The alkaline base stock surface sized with the 40 WF OSA waxy reduced porosity twice as effectively as the 80 WF hydroxyethylated corn. It is noted that surface size starch that helps to reduce paper porosity tends to form a more continuous, defect-free film. This continuous film being comprised of a generally ink receptive polymer, would be more able to capture the ink droplets as they are applied to the paper, preventing their migration through the Z-direction (or thickness) of the paper as well as preventing migration along the papers surface (also called feathering).
- Using the same surface sizing methods as in Example 1, an alkaline base stock having an internal sizing level of 200 seconds (as per TAPPI Test Method T 530 pm - 89, "Size Test For Paper by Ink Resistance ("Hercules Method")) was surface-sized with 10% dispersions of both a hydroxyethylated corn as well as a 55 WF waxy starch reacted with 5% of DDSA (dodecenyl succinic anhydride). The results of this study are tabulated below:
Starch Description % Solids 65°C Brookfield (cps) mPa.s Gurley Density - Seconds (as per TAPPI T460) 80 WF hydroxyethylated corn 10.0 36 15.3 55 WF DDSA Waxy 10.0 200 174.8 - Compared to the alkaline base stock surface sized with the 80 WF hydroxyethylated corn, the alkaline base stock surface sized with the 55 WF DDSA waxy gave over ten times higher density value in seconds (as per TAPPI T460).
- Using the same surface sizing methods as in Example 1, an alkaline base stock having an internal sizing level of 200 seconds (as per TAPPI Test Method T 530 pm -89, noted above) and a CC filer content of 11.8% was surface-sized with 10% dispersions of either an 80 WF oxidized corn starch or a 40 WF waxy starch reacted with 3% OSA. The results of this study are tabulated below.
Starch Description % Solids 65°C Brookfield (cps) mPa.s Gurley Density Seconds (as per TAPPI T460) 80 oxidized corn 10.0 36 33.1 40 WF OSA Waxy 10.0 96 60.8 - Compared to the alkaline base stock surface sized with the 80 WF oxidized corn starch, the alkaline base stock surface sized with the 40 WF OSA waxy gave nearly twice the density value in seconds (as per TAPPI T460).
- This example indicates that paper surface-sized with a layer comprised of a starch substituted with selected hydrophobic groups that is applied at a low-shear viscosity of at least 50 mPa.s (cps at 65°C)) will reduce paper porosity, as compared to paper surface-sized with starches that are not substituted with such groups.
- Using the same surface sizing method and alkaline base stock as in Example 1, surface-sizing was performed with blends of cationic starch (reacted with a tertiary amine group) (Cat.) and a starch reacted with OSA. The nitrogen level (of the cationic starches), the OSA level, the percent of cationic starch in the blend (the balance of the blend is the percent of OSA-treated starch), the fluidity (WF) of the cationic, the WF of the OSA (or hydrophobic) starch and the percent solids of the dispersion applied to the paper were varied as per a two-factor experimental design. The sample sized paper sheets were then evaluated as follows. Gurley density was determined for each sample sheet as in Example 1. Sample sheets were printed on a Hewlett-Packard DeskJet 500C ink-jet printer using a test pattern provided by Hewlett-Packard. On this pattern were a series of three 1 inch squares, two of which were presented at maximum coverage of ink (100%). The optical density for each sample sheet was measured on a MacBeth Densitometer with the results shown below.
Cat. Starch WF Cat. Starch % N Hydrophobic Starch WF % OSA Treatment of Hydrophobic Starch % Cat. Starch In Blend % Total Solids Brookfield Visc. (100 RPM) @ 65°C Gurley density (Sec) Optical Density Solid Black Print (100%) n/a n/a 40 3 0 6 68 13.50 1.15 n/a n/a 40 3 0 10 108 25.38 1.26 70 0.2 70 3 70 10 72 10.75 1.11 70 0.2 70 3 70 6 40 8.56 1.11 40 0.4 40 3 70 10 220 15.73 1.11 70 0.4 70 6 70 10 120 14.93 1.11 70 0.4 70 6 70 6 56 11.44 1.11 40 0.2 40 6 70 6 100 11.20 1.11 40 0.2 40 6 70 10 480 20.96 1.11 40 0.4 40 3 70 6 118 10.15 1.11 70 0.2 40 3 40 6 60 9.70 1.11 70 0.2 40 3 40 10 10 13.15 1.11 40 0.4 70 3 40 6 76 10.68 1.11 40 0.4 70 3 40 10 156 12.70 1.11 70 0.4 40 6 40 6 108 16.22 1.11 70 0.4 40 6 40 10 266 25.73 1.11 40 0.2 70 6 40 6 66 18.02 1.10 40 0.2 70 6 40 10 124 22.29 1.11 Blank (un-surface-sized sheet) 5.5 1.19 - This test data shows that a hydrophobically modified starch, in accordance with this invention, reduces paper porosity (Gurley Density) when applied at higher Brookfield viscosities. Additionally, this data shows that the optical density of a solid black printed box was highest when only the hydrophobically substituted starch was used at a high viscosity in place of a blend of cationic starch and hydrophobically substituted starch. Blends of cationic and hydrophobic starch, even when applied at a viscosity above 50 cps, did not improve the optical density of the black area, compared to the unsurface-sized base sheet.
- Thus, in order to improve ink-jet print quality, it is necessary to use the selected hydrophobic starches of this invention at high Brookfield application viscosities.
Claims (10)
- A method for preparing an ink-jet recording sheet with improved ink-jet print quality comprising:a) providing a recording sheet substrate,b) forming a sizing composition comprising an aqueous dispersion of a hydrophobic starch ester or starch ether derivative wherein the ester or ether substituent comprises a saturated or unsaturated hydrocarbon chain of 6 to 22 carbon atoms having a degree of substitution (DS) of from 0.03 to 0.1 and the starch containing sizing composition has a Brookfield viscosity of at least 50 mPa.s (cps) at 65°C and an alkaline pH of from 7.5 to 10.5,c) applying said sizing composition to said recording sheet substrate, andd) drying said substrate to provide an ink-jet recording sheet.
- The method of Claim 1 wherein the starch containing sizing composition has a Brookfield viscosity of 50 to 500 mPa.s (cps) at 65°C.
- The method of Claim 2 wherein the aqueous dispersion comprises from about 1 to 20% by weight of the derivative in water.
- The method of Claim 1 wherein the recording sheet substrate is paper.
- The method of Claim 4 wherein R1 is an alkyl, alkenyl, aryl, aralkyl or aralkenyl group wherein the starch derivative has a Brookfield viscosity of 50 to 500 mPa.s (cps) at 65°C and a degree of substitution of 0.03 to 0.07.
- The method of Claim 6 wherein R1 is an alkyl or alkenyl group of 8 to 20 carbon atoms and the aqueous dispersion comprises from about 1 to 20% by weight of the starch derivative in water.
- The method of Claim 7 wherein the starch derivative has a Brookfield viscosity of 100 to 300 mPa.s (cps) at 65°C.
- The method of Claim 8 wherein the recording sheet substrate is alkaline grade paper and the aqueous dispersion comprises from about 5 to 12% by weight of the starch derivative in water.
- The ink-jet recording sheet prepared by the method of any of the preceding claims.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US56609995A | 1995-12-01 | 1995-12-01 | |
US566099 | 1995-12-01 |
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EP0776767A1 EP0776767A1 (en) | 1997-06-04 |
EP0776767B1 true EP0776767B1 (en) | 1999-06-16 |
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Application Number | Title | Priority Date | Filing Date |
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EP19960118788 Expired - Lifetime EP0776767B1 (en) | 1995-12-01 | 1996-11-22 | Ink-jet recording sheet and a method for its preparation |
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EP (1) | EP0776767B1 (en) |
JP (1) | JPH09175012A (en) |
AU (1) | AU7197496A (en) |
BR (1) | BR9605763A (en) |
CA (1) | CA2191116A1 (en) |
DE (1) | DE69602910T2 (en) |
ES (1) | ES2134553T3 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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MY125712A (en) | 1997-07-31 | 2006-08-30 | Hercules Inc | Composition and method for improved ink jet printing performance |
US6372361B1 (en) * | 2000-07-07 | 2002-04-16 | National Starch And Chemical Investment Holding Corporation | Coating for paper products |
US8017249B2 (en) * | 2007-02-13 | 2011-09-13 | Tate & Lyle Ingredients Americas Llc | Starch-containing compositions for use in imparting oil or grease resistance to paper |
US8962092B2 (en) * | 2013-01-30 | 2015-02-24 | Corn Products Development, Inc. | Paper sizing using an agent containing uniformly bound octenyl succinic anhydride groups made by the reaction of octenyl succinic anhydride onto a dispersed waxy starch |
US10837142B2 (en) | 2018-12-14 | 2020-11-17 | Sappi North America, Inc. | Paper coating composition with highly modified starches |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2661349A (en) | 1949-02-18 | 1953-12-01 | Nat Starch Products Inc | Polysaccharide derivatives of substituted dicarboxylic acids |
US2876217A (en) | 1956-12-31 | 1959-03-03 | Corn Products Co | Starch ethers containing nitrogen and process for making the same |
US3992432A (en) | 1967-04-05 | 1976-11-16 | Continental Oil Company | Phase transfer catalysis of heterogeneous reactions by quaternary salts |
USRE28809E (en) | 1971-06-24 | 1976-05-11 | National Starch And Chemical Corporation | Preparation of starch esters |
US3720663A (en) | 1971-06-24 | 1973-03-13 | Nat Starch Chem Corp | Preparation of starch esters |
US4020272A (en) | 1975-12-22 | 1977-04-26 | National Starch And Chemical Corporation | Preparation of starch esters |
US4255754A (en) | 1979-03-19 | 1981-03-10 | Xerox Corporation | Differential fiber optic sensing method and apparatus for ink jet recorders |
US4499116A (en) | 1983-01-03 | 1985-02-12 | National Starch And Chemical Corporation | Imitation cheese products containing modified starch as partial caseinate replacement and method of preparation |
US4500895A (en) | 1983-05-02 | 1985-02-19 | Hewlett-Packard Company | Disposable ink jet head |
US4513298A (en) | 1983-05-25 | 1985-04-23 | Hewlett-Packard Company | Thermal ink jet printhead |
US4698123A (en) | 1986-11-12 | 1987-10-06 | Xerox Corporation | Method of assembly for optical fiber devices |
US4751517A (en) | 1987-02-02 | 1988-06-14 | Xerox Corporation | Two-dimensional ink droplet sensors for ink jet printers |
US4794409A (en) | 1987-12-03 | 1988-12-27 | Hewlett-Packard Company | Ink jet pen having improved ink storage and distribution capabilities |
JP3213630B2 (en) * | 1991-07-25 | 2001-10-02 | 三菱製紙株式会社 | Inkjet recording sheet |
SE502545C2 (en) * | 1992-07-07 | 1995-11-13 | Eka Nobel Ab | Aqueous compositions for bonding paper and process for making paper |
US5368690A (en) * | 1992-12-23 | 1994-11-29 | National Starch And Chemical Investment Holding Corporation | Method of papermaking using crosslinked cationic/amphoteric starches |
-
1996
- 1996-11-22 CA CA 2191116 patent/CA2191116A1/en not_active Abandoned
- 1996-11-22 ES ES96118788T patent/ES2134553T3/en not_active Expired - Lifetime
- 1996-11-22 EP EP19960118788 patent/EP0776767B1/en not_active Expired - Lifetime
- 1996-11-22 DE DE1996602910 patent/DE69602910T2/en not_active Expired - Fee Related
- 1996-11-26 AU AU71974/96A patent/AU7197496A/en not_active Abandoned
- 1996-11-29 BR BR9605763A patent/BR9605763A/en active Search and Examination
- 1996-12-02 JP JP8321907A patent/JPH09175012A/en active Pending
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DE69602910D1 (en) | 1999-07-22 |
EP0776767A1 (en) | 1997-06-04 |
AU7197496A (en) | 1997-06-05 |
ES2134553T3 (en) | 1999-10-01 |
BR9605763A (en) | 1998-08-25 |
DE69602910T2 (en) | 1999-11-25 |
CA2191116A1 (en) | 1997-06-02 |
JPH09175012A (en) | 1997-07-08 |
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